Modeling the Influence of Molecular Interactions on the Vaporization of Multi-component Fuel Sprays

Qi Jiao, Youngchul Ra, Rolf D. Reitz

Motivation

Funding Sponsors U.S. DOE& Sandia National Labs

Verification of the model Binary component fuel: benzene + ethanol
T-x phase diagram
benzene+ethanol
80 78 76 74 72 70 68 0.0 0.2 0.4 0.6 0.8 1.0
noUNIFAC UNIFAC

Spray cases: ethanol+gasoline

Tamb=495.51K Pamb=7.36bar

Preferential vaporization of real fuels (diesel, gasoline, bio-diesel, JP8) captured by multicomponent fuel vaporization models (DMC, CMC, DC) 1. Initial boiling point (IBP), final boiling point (FBP) 2. Vaporization sequence 3. Combustion process, emissions formation Ideal-mixing using Raoults Law in current DMC KIVA code misses the azeotropic behavior of mixtures
composed of polar components like ethanol and benzene

Temperature [ C]

E00
0.025 fuel injected
1.0x10
-2

E00 C2 C3 C4 C5 C6

xbenzene

experiment [1]

simulation
fuel mass [g]

0.020 E00 0.015 vapor@noUNIFAC vapor@UNIFAC

8.0x10

-3

Vapor mass [g]

distillation curve
81
noUNIFAC benzene+ethanol
B00 B20 B40 B50 B60 B70 B80 B100

6.0x10

-3

Temperature [ C]

Objective
Molecular interactions are taken into account to treat non-ideal mixing under vapor-liquid equilibrium conditions by implementing the UNIFAC model into a discrete multi-component fuel vaporization code.
ln i ln i
combinatorial

79 78 77 0.0

Temperature [ C]

80

0.2

0.4 0.6 0.8 Volume distilled

1.0

86 84 82 80 78 76 74 72 70 68 66 0.0

UNIFAC benzene+ethanol
B00 B20 B40 B50 B60 B70 B80 B100

0.010

4.0x10

-3

0.005

2.0x10

-3

0.000 0.0000

0.0005

0.0010

0.0015

0.0020

0.0025

0.0 0.0000

0.0005

0.0010

0.0015

0.0020

0.0025

E10
0.025 fuel injected

Time [s]

Time [s]

1.0x10 9.0x10

-2

E10

0.2

0.4 0.6 0.8 Volume distilled

1.0
0.020 E10

-3

8.0x10

-3

fuel mass [g]

0.015

vapor@noUNIFAC vapor@UNIFAC

Vapor mass [g]

ideal-mixing (noUNIFAC): without the non-ideal mixing (UNIFAC): with the consideration of molecular interactions consideration of molecular interactions

7.0x10 6.0x10 5.0x10 4.0x10 3.0x10

-3

-3

C1 C2 C3 C4 C5 C6

-3

Multi-component fuel: ethanol+gasoline

T-x phase diagram @ simulation
80 ethanol & 9-component surrogate for gasoline Pamb=1bar
noUNIFAC UNIFAC

0.010

-3

-3

0.005

2.0x10 1.0x10

-3

ln i

residual

-3

distillation curve @ experiment [2]

0.000 0.0000

0.0

0.0005

0.0010

0.0015

0.0020

0.0025

0.0000

0.0005

0.0010

0.0015

0.0020

0.0025

Temperature [ C]

Interactions between functional groups Differences in size and shape of molecules

xi Pva p , i Pm

E85
0.025 fuel injected 0.020

Time [s]
2.0x10 1.8x10 1.6x10
-3

Time [s]

75 70 65

E85
-3 -3

fuel mass [g]

60 55 50 0.0 0.2 0.4 0.6 0.8 1.0

0.015

vapor@noUNIFAC vapor@UNIFAC

Vapor mass [g]

E85

1.4x10 1.2x10 1.0x10 8.0x10 6.0x10 4.0x10

-3

-3

-3

C1 C2 C3 C4 C5 C6

i x L ,i

-4

0.010

-4

xethanol

-4

0.005
2.0x10
-4

Where
140
noUNIFAC

distillation curve @ simulation

140
UNIFAC

0.0

0.000 0.0000

0.0000
0.0005 0.0010 0.0015 0.0020 0.0025

0.0005

0.0010

0.0015

0.0020

0.0025

Time [s]

Time [s]

Temperature [ C]

100

Temperature [ C]

i is the activity coefficient for component i . Pm is the total mixture pressure or the ambient atmospheric

9comp-surrogate for gasoline gasoline+ethanol 120

0

9comp-surrogate for gasoline gasoline+ethanol 120

0

Note: the black line indicating ethanol is not shown completely because it has far more vapor mass than other components.

Tamb=500K Pamb=1bar E00 E10 E20 E40 E50 E60 E85 E90 E100

Tamb=500K Pamb=1bar E00 E10 E20 E40 E50 E60 E85 E90 E100

100

Ongoing work
Application to cold start in diesel engines and low temperature combustion especially with ethanol should be studied. The application of the UNIFAC model to surrogates for other real fuels like diesel, bio-diesel and JP8 are needed.
Reference:
[1]. Hadler, A.B., Ott, L. S., Bruno, T. J. , Study of Azeotrope Mixtures with the Advanced Distillation Curve Approach, Fluid Phase Equilib. 2009, 281, 49-59. [2]. Andersen V.F., Andersen J.E., Wallington T.J., Mueller S.A., Nielsen O.J., Energy&Fuels 2010, 24, 2683-2691.

pressure. Pva p , i is the vapor pressure of the pure component i . x L , i is the mole fraction of the component in the liquid phase. x i is the mole fraction of the gas phase for each component .

80

80

60

60

40 0 20 40 60 80 100 Volume [%]

40 0 20 40 60 80 100 Volume [%]

ideal-mixing (noUNIFAC): without the consideration of molecular interactions

non-ideal mixing(UNIFAC): with the consideration of molecular interactions

Note: Ref. [2] did not provide the chemical composition of the base gasoline used in the experiments, this makes matching the distillation curve and the properties of gasoline difficult. However, it is of interest to see whether the UNIFAC model can capture the important characteristics seen by adding different amounts of ethanol to gasoline .

UNIVERSITY OF WISCONSIN - ENGINE RESEARCH CENTER